Process for producing group III-V compound semiconductor and group III-V compound semiconductor

Abstract: A process for producing a Group III-V compound semiconductor, which comprises: (1) forming a thin crystal film of A₁ III As w P 1-w , wherein A₁ III represents a Group III element with an Al composition of less than 0.3, and 0.5 < w ≦ 1, on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; forming thereon a thin crystal film of B III As, wherein B III represents a Group III element with an Al composition of not less than 0.3; and forming thereon a thin crystal film of C₁ III As x P 1-x , wherein C₁ III represents a Group III element with an Al composition of less than 0.3, and 0 ≦ x < 0.5; or (2) forming a thin crystal film of A₂ III As u P 1-u , wherein A₂ III represents a Group III element with an In composition of not less than 0.3, and 0 ≦ u ≦ 1, on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; forming thereon a thin crystal film of B III As, wherein B III represents a Group III element with an Al composition of not less than 0.3; and forming thereon a thin crystal film of C₂ III As z P 1-z , wherein C₂ III represents a Group III element and 0 ≦ z ≦ 1.

Description: The present invention relates to a process for producing a Group III-V compound semiconductor and to a Group III-V compound semiconductor. These semiconductors may be used for various semiconductor devices such as laser diodes, light-emitting diodes and high electron-mobility transistors. The following methods have been known for crystal growth of the elements used for semiconductor devices: (i) a crystal of C 1 III As x P 1-x (C 1 III : one or more Group III elements, 0 ≤ x < 0.5) is directly grown on A 1 III As w P 1-w (A 1 III : one or more Group III elements with an Al content of less than 0.3, 0.5 < w ≤ 1) formed on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; and (ii) a crystal of A 2 III As u P 1-u (A 2 III : one or more Group III elements with an In content of not less than 0.3, 0 ≤ u ≤ 1) is grown on a semiconductor crystal substrate or on an epitaxial film grown on said substrate, and after an interruption of crystal growth in which a heating step is required, a C 2 III As z P 1-z crystal (C 2 III : one or more Group III elements, 0 ≤ z ≤ 1) is grown directly on the A 2 III As u P 1-u . For crystal growth of (Al y Ga 1-y ) 0.5 In 0.5 P (0 ≤ y ≤ 1), which is a material used in visible laser diodes or visible light emitting diodes, a GaAs buffer layer is generally grown on a GaAs substrate and the crystal material is directly grown on the GaAs buffer layer by a MOVPE (metal organic vapor phase epitaxy) technique. However, the direct growth of a (Al y Ga 1-y ) 0.5 In 0.5 P crystal on the GaAs buffer layer formed on a GaAs substrate involves problems in that substitution takes place between the As in the GaAs crystal and the P in the vapor phase causing interfacial defects, thereby making it impossible to obtain an AlGaInP crystal with a good quality. Especially in the growth of an AlGaInP crystal with a high Al content, it is vital to carry out the crystal growth at a high temperature (not less than 700°C) for preventing contamination of the crystal with oxygen, to reduce the influence of the interfacial defects due to substitution between the As in the GaAs crystal and the P in the vapor phase. Growth of the GaAs buffer layer on a semiconductor substrate is preferably carried out at a low temperature of less than 700°C for minimizing diffusion of impurities from the substrate crystal into the epitaxial crystal layer. Further, if the buffer layer of A 2 III As u P 1-u has a high In content, when the crystal growth is carried out at a high temperature a large quantity of In has to be supplied since the efficiency of In incorporation into the crystal is reduced. Thus, it is advantageous to carry out the crystal growth of the A 2 III As u P 1-u buffer layer at a low temperature (less than 700°C). On the other hand, the light-emitting layer of a light-emitting semiconductor device needs to have a high luminous efficiency as well as a good crystal quality. Therefore, it is generally preferred that the growth of the light-emitting layer is carried out at a high temperature. Especially in the case where the light-emitting layer contains Al (for example, a layer composed of AlGaInP or AlGaAs), when the crystal growth is carried out at a low temperature (less than 700°C), the Al element which is one of components of the layer, reacts with the oxygen remaining in a trace amount in the growth gas. This causes contamination of the crystal with the oxides or occurrence of micro-defects, so that it is impossible to obtain a crystal with a high luminous efficiency and a good quality. Therefore, it is preferred that the growth of AlGaInP or AlGaAs is carried out at a high temperature (not less than 700°C) so as to prevent the grown crystal from being contaminated with the Al and oxygen reaction product. For these reasons, in the crystal growth method in which a A 2 III As u P 1-u crystal is first grown on a substrate and then a AlGaInP or AlGaAs crystal is grown on the A 2 III As u P 1-u buffer layer, it is usual practice to carry out the growth of the A 2 III As u P 1-u crystal at a low temperature (around 660°C) and then elevate the temperature to conduct the growth of the AlGaInP or AlGaAs crystal at a high temperature of not less than 700°C. In this method, however, a part of the In in the A 2 III As u P 1-u crystal grown at a low temperature is desorbed in the course of heating due to the high vapor pressure, thereby causing surface defects in the grown crystal. The AlGaInP or AlGaAs crystal grown thereon inherits these defects, so that it is impossible to obtain the desired high-quality AlGaInP or AlGaAs crystal. The present invention seeks to provide a semiconductor having a thin crystal film of C 1 III As x P 1-x or C 2 III As z P 1-z which is substantially free of contamination with impurities or micro-defects. The present invention seeks to provide a high-reliability and high-performance semiconductor device using said crystal film. As a result of intensive studies for overcoming these technical problems, it has been found that by growing a thin crystal film of B III As (B III : one or more Group III elements with an Al content of not less than 0.3) as a protective film on a thin film of A 1 III As w P 1-w or A 2 III As u P 1-u formed on a semiconductor crystal substrate or on an epitaxial layer grown on the semiconductor crystal substrate, it is possible to prevent said interfacial defects, especially the crystal defects caused in the heating step, and to obtain a good crystal lattice-matched to the underlying layer. The present invention provides a process for producing a Group III-V compound semiconductor, which comprises: (1) forming a thin crystal film of A 1 III As w P 1-w , wherein A 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0.5 < w ≤ 1, on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; forming thereon a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3, and forming thereon a thin crystal film of C 1 III As x P 1-x , wherein C 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0 ≤ x < 0.5; or (2) forming a thin crystal film of A 2 III As u P 1-u , wherein A 2 III represents one or more Group III elements with an In content of not less than 0.3, and 0 ≤ u ≤ 1, on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; forming thereon a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3; and forming thereon a thin crystal film of C 2 III As z P 1-z, wherein C 2 III represents Group III elements and 0 ≤ z ≤ 1. The present invention also provides a Group III-V compound semiconductor comprising: (1) a thin crystal film of A 1 III As w P 1-w, wherein A 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0.5 < w ≤ 1, formed on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3, formed on the A 1 III As w P 1-w film; and a thin film of C 1 III As x P 1-x , wherein C 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0 ≤ x < 0.5, formed on the B III As film; or (2) a thin film of A 2 III As u P 1-u , wherein A 2 III represents one or more Group III elements with an In content of not less than 0.3, and 0 ≤ u ≤ 1, formed on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3, formed on the A 2 III As u P 1-u film; and a thin film of C 2 III As z P 1-z , wherein C 2 III represents one or more Group III elements and 0 ≤ z ≤ 1, formed on the B III As film. The present invention additionally provides a Group III-V compound semiconductor as defined above which is obtainable by the process defined above. The present invention further provides a laser diode, light-emitting diode or transistor comprising a semiconductor as defined above. Fig. 1 is a schematic illustration of the structure of the semiconductor of Example 1 fabricated according to the process of the present invention. Fig. 2 is a schematic illustration of the structure of the semiconductor of Example 2 fabricated according to the process of the present invention. In the present invention, a thin crystal film of A 2 III As u P 1-u is formed on a semiconductor crystal substrate or on an epitaxial layer grown on the semiconductor crystal substrate, preferably at a temperature of less than 700°C, more preferably 600 to 680°C, for the reason mentioned above. Examples of A 1 III As w P 1-w usable in present invention which contain one or more Group III elements with an Al content of less than 0.3 include InAsP, AlInAsP, AlInAs, InAs, AlGaAs, GaAs and GaAsP. Examples of A 2 III As u P 1-u which contain one or more Group III elements with an In content of not less than 0.3 include InAsP, AlInAsP, AlInAs, InAs, AlInP, GaInP, AlGaInP, InGaAs and InGaAsP. The thickness of each thin crystal film of A 1 III As w P 1-w and A 2 III As u P 1-u depends on the purpose of use of the thin crystal film. In case it is used as a buffer layer, the thickness of each film is preferably from 0.1 to 2 µm. The semiconductor crystal substrate or the epitaxial layer grown on the substrate used in the present invention is preferably one which has no possibility of causing a lattice mismatch between the A 1 III As w P 1-w or A 2 III As u P 1-u layer and the semiconductor crystal substrate or the epitaxial layer grown thereon. More preferably, the substrate or the epitaxial layer grown thereon is of the same composition as the A 1 III As w P 1-w or A 2 III As u P 1-u layer. The thickness of the semiconductor crystal substrate depends on the purpose of use thereof, but is preferably from 100 to 500 µm. The thin crystal film of B III As used in the present invention serves as a protective layer for inhibiting substitution between the As in the underlying layer of A 1 III As w P 1-w crystal and the P in the vapor phase or desorption of In in the A 2 III As u P 1-u crystal layer. The lower limit of thickness of the B III As crystal film is 0.5 nm, preferably 2 nm, in the case of a AlAs crystal film. Since the B III As crystal film acts as a protective layer in spite of its small thickness such as mentioned above, application of this B III As layer does not substantially influence the electrical and optical properties of the product. The upper limit of thickness of the B III As crystal film can be raised to a level close to the critical thickness which does not cause dislocation due to lattice mismatch, but for economic reasons the upper limit of the thickness of the B III As crystal film is 10 µm. Thus, the film thickness is from 0.5 nm to 10 µm, preferably from 2 nm to 5 µm, more preferably 5 nm to 2 µm. The thin film of B III As is grown at the same temperature as that used for its underlying layer so that there is no desorption of a part of As or In from the underlying layer of the A 1 III As w P 1-w or A 2 III As u P 1-u crystal during the growth to cause surface defects. AlGaAs and AlAs can be mentioned as typical examples of B III As. The Al content in the Group III elements in B III As is not less than 0.3, preferably not less than 0.45. For producing a salient effect, the Al content is preferably not less than 0.55, and in the case where the film thickness is reduced, the content is preferably not less than 0.7. When growing C 1 III As x P 1-x of a desired composition on the B III As layer, there can be obtained a C 1 III As x P 1-x layer with a very good crystal quality. Growth of C 2 III As z P 1-z on the B III As layer is carried out at a higher temperature than conventionally used in the case where Al is contained, such as in a AlGaInP or AlGaAs crystal, for the reasons mentioned above. Even when the growth of C 2 III As z P 1-z is carried out at the same temperature as used for the underlying layer, when the crystal growth is interrupted for some reason or other before the C 2 III As z P 1-z crystal is grown, the B III As protective layer proves effective for preventing desorption of the In. The crystal growth mentioned above can be accomplished by a known MOVPE (metal organic vapor phase epitaxy) or MOMBE (metal organic molecular beam epitaxy) technique. It is also possible to employ other known methods such as a VPE (vapor phase epitaxy) or MBE (molecular beam epitaxy) technique. In the crystal growth process according to the present invention, it is possible to prevent desorption of the In from the underlying layer even under high temperatures owing to the application of a thin crystal film of B III As which is grown as an underlying layer before the growth of the C 1 III As x P 1-x or C 2 III As z P 1-z crystal. Also, since As is scarcely desorbed because of the high Al-As bond energy, the B III As, film surface remains free of defects during the heating step. Therefore, even when growth of the C 1 III As x P 1-x or C 2 III As z P 1-z crystal is carried out at a high temperature on the A 1 III As w P 1-w or A 2 III As u P 1-u crystal of the buffer layer having its surface protected with a B III As film, no defect, such as seen in the conventional practice, is induced, and a high-quality crystal well reflecting the growth effect at a high temperature can be obtained. Even when growth of C 2 III As z P 1-z is performed at the same temperature as used for the growth of its underlying layer, when it is necessary to interrupt the crystal growth for some reason or other, the B III As layer proves to be very useful for preventing trouble. The above-described crystal growth process is particularly effective when the substrate crystal is GaAs, GaP, InP or an alloy semiconductor thereof, and an equal effect can be obtained in each case. According to the process of the present invention, substitution between the As in the crystal of A 1 III As w P 1-w on a semiconductor substrate and the P in the vapor phase is inhibited which prevents occurrence of interfacial defects. The thus grown C 1 III As x P 1-x crystal is substantially free of impurities or micro-defects and can therefore serve as a high-quality crystal with a strong photoluminescence intensity. It is also possible to grow the crystal of AlGaInP or AlGaAs at an optimal temperature higher than used for forming a buffer layer on a semiconductor substrate. The thus grown AlGaInP or AlGaAs crystal has few impurities or micro-defects and can serve as a high-quality crystal with a strong photoluminescence intensity. Examples The present invention is now further described in the following Examples thereof. Example 1 An undoped double heterostructure (DH structure) was produced according to the MOCVD technique as shown in Fig. 1. First, GaAs crystal 2 was grown to a thickness of 0.5 µm to form a buffer layer on a GaAs (100) substrate 1. On this buffer layer was grown a 1.5 nm-thick AlAs film 3 to form a surface protective layer. Growth of the GaAs buffer layer and the AlAs film was carried out under the following conditions: temperature = 700°C, pressure = 10 2 hPa, V:III molar ratio = 50:1, growth rate = 2.0 µm/hr. On said protective layer 3 were grown successively a 0.5 µm-thick (Al 0.7 Ga 0.3 ) 0.5 In 0.5 P cladding 4, a 0.1µm-thick (Al 0.7 Ga 0.5 ) 0.5 In 0.5 P active layer 5 and a 0.2 µm-thick (Al 0.7 Ga 0.3 ) 0.5 In 0.5 P cladding 6, under the conditions of a temperature of 700°C, a pressure of 102 hPa, a V:III molar ratio of 450:1 and a growth rate of 1.0 µm/hr. Comparative Example 1 The same procedure as Example 1 was carried out except that no AlAs film 3 was provided. The DH structure grown according to the method of the present invention generated an approximately 10 times stronger photoluminescence intensity than the DH structure formed according to the conventional crystal growth method (Comparative Example 1). Example 2 As shown in Fig. 2, a 1.5 nm-thick AlAs film 2 was grown to form a surface protective layer on a GaAs (100) substrate 1 according to the MOVPE technique under the conditions of a temperature of 660°C, a pressure of 10 2 hPa, a V:III molar ratio of 50:1 and a growth time of 7 seconds. On this surface protective layer a Ga 0.5 In 0.5 P crystal 3 was grown at a temperature of 660°C to a thickness of 0.2 µm to form a buffer layer on the AlAs film 2 under the conditions of a pressure of 10 2 hPa, a V:III molar ratio of 450:1 and a growth rate of 1.0 µm/hr. On this buffer layer 3 was grown a 1.5 nm thick AlAs film 4 at a temperature of 660°C to form a surface protective layer under the conditions of a pressure of 10 2 hPa, a V:III molar ratio of 50:1 and a growth time of 7 seconds. Then the temperature was raised at a rate of 5°C/min till it reached 700°C. As the gas atmosphere during heating, hydrogen gas was flowed along with A 5 H 3 gas at 10 vol% based on hydrogen gas for preventing release of the As from the AlAs. Then (Al 0.5 Ga 0.5 ) 0.5 In 0.5 P crystal 5 was grown to a thickness of 0.5 µm under the conditions of a temperature of 700°C, a pressure of 10 2 hPa, a V:III molar ratio of 450:1 and a growth rate of 1.0 µm/hr. Comparative Example 2 (Al 0.5 Ga 0.5 ) 0.5 In 0.5 P sample structure was grown by following the procedure of Example 2 except that no AlAs film 3 was provided. The sample structure provided with the AlAs layer generated about a 10-fold stronger photoluminescence intensity than the sample structure having no AlAs layer.

Claims: A process for producing a Group III-V compound semiconductor, which comprises: (1) forming a thin crystal film of A 1 III As w P 1-w , wherein A 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0.5 < w ≤ 1, on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; forming thereon a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3; and forming thereon a thin crystal film of C 1 III As x P 1-x , wherein C 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0 ≤ x < 0.5; or (2) forming a thin crystal film of A 2 III As u P 1-u , wherein A 2 III represents one or more Group III elements with an In content of not less than 0.3, and 0 ≤ u ≤ 1, on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; forming thereon a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3; and forming thereon a thin crystal film of C 2 III As z P 1-z , wherein C 2 III represents one or more Group III elements and 0 ≤ z ≤ 1. A process according to claim 1 wherein the Group III element is at least one element selected from Al, Ga and In. A Group III-V compound semiconductor comprising: (1) a thin crystal film of A 1 III As w P 1-w , wherein A 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0.5 < w ≤ 1, formed on a semiconductor crystal substrate or on an epitaxial film grown on said substrate; a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3, formed on the A 1 III As w P 1-w film; and a thin film of C 1 III As x P 1-x , wherein C 1 III represents one or more Group III elements with an Al content of less than 0.3, and 0 ≤ x < 0.5, formed on the B III As film; or (2) a thin film of A 2 III As u P 1-u , wherein A 2 III represents one or more Group III elements with an In content of not less than 0.3, and 0 ≤ u ≤ 1, formed on a semiconductor crystal substrate or on an epitaxial film grown on the said substrate; a thin crystal film of B III As, wherein B III represents one or more Group III elements with an Al content of not less than 0.3, formed on the A 2 III As u P 1-u film; and a thin film of C 2 III As z P 1-z , wherein C 2 III represents one or more Group III elements, and 0 ≤ z ≤ 1, formed on the B III As film. A semiconductor according to claim 3 wherein the thickness of the thin crystal film of B III As is 0.5 nm to 10µm. A semiconductor according to claim 4 wherein the thickness of the thin crystal film of B III As is 2 nm to 5µm. A semiconductor according to any one of claims 3 to 5 wherein the Group III element is at least one element selected from Al, Ga and In. A semiconductor according to claim 6 wherein B III As is AlGaAs or AlAs. A semiconductor according to any one of claims 3 to 7 which is obtainable by the process of claim 1. A laser diode, light-emitting diode or transistor comprising a semiconductor as defined in any one of claims 3 to 7.

Inventors: GOTO HIDEKI, HOSOI NOBUYUKI, SHIMOYAMA KENJI, GOTO, HIDEKI, HOSOI, NOBUYUKI, SHIMOYAMA, KENJI
Applicants: MITSUBISHI CHEM CORP, MITSUBISHI CHEMICAL CORPORATION
Application year: 1994
Main classification: H01L21
IPC codes: H01L33, H01S5, C30B25, H01L29